Esters of secondary alcohols



Patented July. 21,

UNITED STATES PATENT OFFICE I ROBERT E. VAN SOEAACK, JR., OF EVANS'I'ON, ILLINOIS, ASSIGNOR TO .VAN SCHAAOK BROS..OH EMICAL WORKS, INC., OF CHICAGO, ILLINOIS, A CORPORATION OF ILLI- NOIS EsrERs or SECONDARY ALcoEoLs Ito-Drawing.

atoms to the'molecule with dibasic organic to give the corresponding succinates. Likeacids. Examples illustrating the invention follow.

ooo.on cH. oHo|.om

I ooriwmwmaoa.

Methyl-n-hexyl-methyl phthalate.

" oooomomywmncn,

Methyl-n-hexyl-methyl hydrogen phthalate. v I

CO0.0H(CHa).(CHI)I.OHt I 00.0m- I I Methyl-n-hexyl-methyl ethyl phthalate. a. In each of the above examples'the phthalate radical, I

00., I I may be replaced by the succinate radical,

. oHLooo.

n,.o oo..

wise,-the invention includes the corresponding esters of tartaric, citric, maleic, trimesic, or other dibasic' or polybasic organic acid. Also, the methyl-n-hexyl -methyl radical in the type formulas above may be substituted by radicals of other secondary aliphatic alcohols that contain more than six carbon atoms to' the molecule, as, for example, methyl-n-amyl-carbinol, methyl-isoamylcarbinol, ethyl-n-butyl-carbinol, ethyl-isobutyl --carbinol, methyl isohexyl carbinol, ethyl-n amylcarbinol, ethyl-isoamyl-carbinol, propyl-n-butyl carbinol, ropyl-isobutyl-carbinol, isopropyl-isobuty -carbinol, methyl-n-heptyl-carbinol or other secondary 'nonyl alcohol, or methyl-n-octyl-carbinol or other secondary decyl a1cohol. Also, the ethyl radical shown in the formula above may be replaced b another akyl' group, as, for example, met yl, propyl, isopropyl, butyl, secondary butyl, amyl, or isoamy The examples above are given for-the urose of illustration and not limitation oi the lnvention. The invention comprises the Application filed September 29, 1928. Serial'No. 309,365.

acid or neutral esters of a polybasic organic I I "'-acid in which the hydrogen of at least one carboxyl group has been replaced by the radical of a secondary.aliphatic'alcohol that contains more than six carbon atoms to the molecule. I

To prepare the neutral esters one may esterify the polybasic acid with an excess of the alcohol.

Examples illustrating methods of preparation follow.

A mixture of 4 parts by weight of succinic acid, 13 of methyl-n-hexylcarbin.ol, 20 of toluol, and of sulfuric acid is submitted to fractionation for a period of 5 hours, the toluol layer of the condensate being returned substantially continuously to the still in order to remove from the still the water formed by I the interaction ofthe acid and the alcohol. The mixture remaining in the still after 5 hours is neutralized by thoroughly agitating with 2 arts of soda ash dissolved in 20 of water, a lowing the mixture to stand, and-then v drawing off the lower layer that forms. After being washed with 40 parts of water, in 2 portions, the oil layer is distilled to remove the toluol and excess of methyl-n-hexyl-carbinol. The remaining oil comprises methyl-n-hexylmethyl succinate,

[CH2.CO0.CH(CH8)-(c als-cHalz- On fractional distillation it boils at 228 C. I

In another preparation, ortho-phthalic acid was substituted for the succinic in the above example. The resulting methyl-n-hexylmethyl phthalate boiled at a temperature above 210 C. at 3 mm. This compound also I is useful as a solvent for certain resins and oils. It is substantially non-volatile at at-' mospheric temperatures. It is a slowly acting solvent for pyroxylin.

Lacquers may be. made that comprise pyroxylin, ester gum or dammar, volatile solvents and diluents, and the neutral ester of olefins I find suitable the fraction of cracked petroleum that distills at 40 to 140 C. I find suitable also the material obtained by subjecting petroleum to cracking at a relatively high temperature,soca1ledvapor-phasecracking, and fractionating, from the product, compounds of boiling point not above 140 0., at atmosphericv pressure. Theconversion of liquid olefins, of boiling point below 140 0.,

in a fraction of cracked petroleum, to the corresponding alcohols may be made by well known methods, as, for example, by treatment with sulfuric acid, dilution with water, distillation, and, finally, fractionation of the oil lzlilyer of the distillate to give a fraction dist' ling below 140 C. that consists chiefly'of hydrocarbons and one distilling above140 C. that comprises most of the alcohols formed. In these higher alcohols, some methyl-nhexyl-carbinol is resent To make an aci ester, there may be used a deficiency of the alcohol as compared to the organic acid, for example, one molecular proportion of a dibasic acid and one molecular proportion of the alcohol, in the presence'of an acid cataylst. A mixed ester may be made, for example, by first preparing an acid ester, as above, and then adding another alcohol, esterfying, neutralizing, and distilling. In such a way, one makes an ester containing the radicals of more thanone alcohol.

The above examples illustrate methods of preparin some of the compounds of my invention. any details may be varied or other entirely difi'erent processes of preparation. may be used without departing from the spirit of the invention. Thus, for example, one may potassium salt of a polybasic acid with a secondary alkyl chloride, said alkyl group containingmore than 6 carbon atoms to the molecule..

branched chain structure, as used in the claims, is intended to mean an alcoholof the type v a cmononmcmhcn, as distinguished from the type cmcnoncmcngmcnnacn,

or v cmcnonmcnmomcm) so In' the-branched chain type at least one of the alkyl group joined to the .OHOH. group is an isoalkyl'radical.

I claim: 1. 'A composition of matter comprising an 05 ester of a polybasic organic acid with a secreflux a solution comprising the sodium or An alcohol that does not? contain a ,s ondary, aliphatic alcohol that contains more than six carbon atoms to the molecule.

2. A composition of matter comprising an ester of a polybasic aliphatic acid with a monohydric aliphatic secondary alcohol that contains more than six carbon atoms to the molecule.

3. A composition of matter comprising an ester of a polybasic organic acid with methyln-hexylcarbinol.

4. A composition of matter comprising an ester of a dibasic organic acid with a secondary, aliphatic alcohol that contains more than six carbon atoms to the molecule.

5. A composition. of matter comprising an ester of a dibasic aliphatic acid with a monohydric aliphatic secondary alcohol that contains more than six carbon-atoms to the molecule.

6. p A composition of matter comprising an ester of succinic acid with a monohydric aliphatic secondary alcohol that contains more than six carbon atoms to the molecule.

7. A composition of matter comprising an ester of a dibasic organic acid with a monotains more than six carbon atoms to the molecule and that does not contain a branched chain structure. 1

8. A composition of matter comprising an ester of a dibasicorganic acid with methyln-hexyl-carbinol.

9. Methyl-n-hexyl-methyl succinate.

10. A composition of matter comprising esters of a dibasic organic acid with the mixture of alcohols corresponding to the olefins of a fraction of cracked gasoline that boils below 140 C. I

11. A composition of matter comprising esters of a dibasic aliphatic acid with the mixture of alcohols corresponding to the olefins of a fraction of cracked gasoline that boils below 140 C. Y

12. A composition of matter comprising esters oi succinic acid with the mixtureof alcohols corresponding to the olefins of a fizgctipjn of cracked gasoline that boils below 13. The esters of a dibasic acid with alcohols corresponding to liquid olefins boiling at 40 to 100 (1, said olefins being derived from a petroleum that has been submitted to vapor-phase cracking.

14. A composition of .matter comprising the grouping of atoms represented by the formula in which R represents a bivalent radical comprising carbon and hydrogen atoms and R represents the radical of a secondary, aliphatic alcohol containing more than six carthe ' p in which R stands for I taining onlyc'arbon' and hydrogen and It stands for the radical of a secondary, ali- I more than six I represents the carbinol.

the

' i cooav 00- in which R a bivalent radical comprising carbon and hydro n atoms and .R A

radical o methyl-n-hexyl- 16. A composition of matter comgrising the grouping of atoms represented formula BQOOJI 00.3

. in which R represents a bivalent radical con- 7 taining carbon and hydrogen and R represents the radical of a secondary, aliphatic alcohol that'contains more than six carbon atoms to the molecule.

- 17. A composition of matter com the grouping of atoms represented by the formula 00.11 coma,

in which R represents a bivalent radical containin carbon and hydrogen and It repre-- sentst cooxy 1 ooa bivalent radical conphatic alcoholthat contains carbon atoms tothemolecul ROBERT SCHAAGK, JR.

grouping of atoms represented by the formula w y the 

